New mixed alcoholates-phenolates of aluminum and a process for the production thereof



fiinited States Patent NEW MIXED ALCOHOLATES-PHENOLATES OF ALUNHNUM ANDA PROESS FOR THE PRO- DUCTION THEREOF Herbert Arnold, Rolf Rebling, andAlbert Erh'ardt, Bielefeld, Germany, assignors to Asta-WerkeAktiengesellschaft Chemische Fahrik, Brackwetle, Germany N Drawing.Application May 12, 1958 Serial No. 734,414

Claims priority, application Germany May 17, 1957 Claims. (Cl. 260-448)The present invention relates to a new mixed alcoholates-phenolates ofaluminum and to a process for the production thereof.

The new mixed alcoholates-phenolates of aluminum provided by the presentinvention correspond to the following Formula I:

)11" I wherein R represents a member of the group consisting of thealkyl radicals with 2-9 carbon atoms and the cyclohexyl radical, Rrepresents a member of the group consisting of the 4-nitrophenyl group,the 2,4-dinitro phenyl group, and the 2,4-dinitro-l-naphthyl group, andR represents a member of the group consisting of the alkyl radicals with2-9 carbon atoms, the cyclohexyl radical, the 4-nitro phenyl group, the2,4-dinitro phenyl group, and the 2,4-dinitro-1-naphthyl group.

A preferred embodiment of the invention provides products of the abovegeneral Formula I wherein R has the same meaning as defined above, Rrepresents the 2,4-dinitro-l-naphthyl-group, and R" represents a memberof the group consisting of the 4-nitro phenyl group, the 2,4-dinitrophenyl group, and the 2,4-dinitro-lnaphthyl group. Preferably R and Rrepresent each a 2,4- dinitro-l-naphthyl-group.

The products of the general Formula I can be prepared by reacting 1 moleof a compound of the general Formula II:

R H wherein R has the same meaning as in the general Formula I, with 1-3moles of a member of the group consisting of the 4-nitro phenol, the2,4-dinitro phenol, and the 2,4-dinitro-1-naphthol and -l-naphthols. Thereaction is preferably carried out in the presence of a solvent beingcapable of dissolving at least part of the reaction components. Assolvents one may for example use benzene, toluene or xylene, alcohols inwhich the aluminum alcoholates used are soluble, chlorinated aliphatichydrocarbons, for example carbon tetrachloride or dichloroethane andhydrogenated or partially hydrogenated aromatic solvents, for exampletetralin. Mixtures of they aforementioned solvents can be used, ifdesired.

The speed of the reaction and the extent to which the the reactionmedium. When an alcohol corresponding to the radical R is used asreaction medium, for example, this replacement takes place practicallyinstantaneously, whereas when an aromatic hydrocarbon, for examplebenzene, is used it is necessary to heat the reaction mixfi 2336,31? Q6Patented May 10, 1960 question or to allow the reaction mixture to standfor a longer period.

When reacting equimolar quantities of the reaction components oneradical R of the compound of the general Formula II is replaced by theradical of the nitro phenol or naphthol. When using two moles of thenitro phenol or naphthol and one mole of the compound of the generalFormula II, two radicals R are replaced by the radical of the nitrophenol or naphthol. In this case an excess of the phenolic startingcomponent may be used since the third radical R is not. displaced evenwhen a large excess of the phenolic component is used.

The new products form colored crystalline compounds which are insolublein most organic solvents and nearly insoluble in water; they do notpossess definite melting points, but decompose when heated to highertemperatures. This is due to the organic/inorganic character of thecompounds in question.

The new products according to our invention can be used therapeuticallyas specific agents against hookworm infections.

The following Table 1 shows the doses that proved to be fully or partlyeffective against the so-called ancylostomiasis of the cat. Thetreatment of the sick animals with the compounds in question Was carriedout in accordance with the following publications:

Erhardt, A.: Testierungsmethode Ancylostorna-wirksamer Praparate undihre therapeutischen Untersuchungen an der Ancylostomiasis der Katze.Deutsche Tropenmedizin. Monatsschrift 42, 108 (1938);

Brumpt, E., Neveu-Lemaire, M. uncl Erhardt, A.: Praktischer Leitfadender Parasitologie des Menschen. 2. Auflage, Springer-Verlag 1951.

examples:

Example IDiisopropyl-[2,4-dinitronaphthyl-(J aluminum alcoholate 4 g. of2,4-dinitro-1-naphthol purified by way of its ammonium salt aredissolved in 20 cc. of warm tetralin. Approximately 6080 cc. of absoluteisopropyl alcohol are then added and a hot filtered solution of 3.49 g.of molten aluminum isopropylate in 10 cc. of tetralin is added dropwisewithout delay to the heated solution while stirring. Orange-coloreddiisopropyl [2,4 dinitronaphthyl-( 1) ]-aluminum alcoholatespontaneously precipitates, and this substance is filtered off withsuction while still hot, washed with absolute ether and dried in vacuo.Yield: 4.8 g., i.e. 74.2% of the theoretical yield.

Example 2.-Di-n-butyl-[2,4-dirzitr0naphthyl-(1 )1- aluminum alcoholate 4g. of .2,4-dinitro-1-naphthol are dissolved in 20 cc. of Warm tetralin,mixed with 60 cc. of absolute n-butanol and heated. A hot solution of4.20 g. of aluminum triture for instance to the boiling point of thesolvent in n-butylate in 10 cc. of tetralin is added to thefirst-mentioned solution while stirring. The result is di-n-butyl-[2,4,-dinitronaphthyl-(l)]-alumium alcoholate in a yield of 5.5 g.(79.1% of the theoretical yield). This product is worked up as describedin Example 1. r A

Example 3.--D'z'is0pr0pyl-[2,4-dinitronaphthyl-(I aluminum alcoholate 5g. of 2,4-dinitro-1-naphthol purified by way of its ammonium salt aredissolved in a mixture of 160 cc. of absolute isopropyl alcohol and 80cc. of dry bfinzene, and a hot solution of 1.46 g. of aluminumtriisopropylate in a mixture of 35 cc. of absolute isopropyl alcohol and15cc. of dry'benzene .is added dropwise without .delay to the heatedsolution while stirring. Orangecolored .diisopropyl-[2,4-dinitronaphthyl-( 1'.) aluminur n alcoholate spontaneouslyprecipitates; this substance is filtered off with suction while stillhot, subjected to extraction while hot with dry benzene, washed withabsolute ether and dried .in a vacuum drier. Yield: 74.2% of thetheoretical yield.

Example-4r-rDi-nsbutyl [,2,4-;dinitrionaphthyl-(1 )1- aluminumalcoholate 517 g. of .'2,4-dinitro-l-naphthol are dissolved in *250 cc.of absolute n-butanol and added dropwise to 2 g. of aluminumtri-n-butylate in 25 cc. of absolute n-butanol while hot and whilestirring. The di-n-butyl-{ZA-din'itronap'hthyl-(l ]-a'luminum alcoholatewhich is formed immediately'precipitates as an orange-coloredprecipitate, which is filtered ofi" with suction while still hot, issubjecte'd'to extraction withdry boiling benzene, washed with absoluteether and dried invacuo. ,Yield: 12g. (60.5% of the theoretical yield).

Example 5 .Ethyl-ibis-[ p-nitrphen0l -aluminum alcoholate Asolution ofg. .of aluminumtriethylatein 50 cc. o'f-dry benzene is quickly addeddropwise to a boiling solution of 15 ",gxof p-nitroPhenol in 1.30 cc.'ofdry henzenewhilestirring, and the mixture is'heated for 2 hours totheboiling-point. 'This results in the precipitation ofethyl-bis-[p-nitrophenol1-aluminum alcoholate, which is filtered ofiwith suction while still not, subjected to extraction while hot with drybenzene, washed with ..absolute ether .and dried in vacuo. Yield: 9.5 g.(88.5% of 'the'theoretical yield) Example6.-Ethyl-bis-[2,4-dinitrophenol]aluminum alcoholate Asolution' of 0.02mol of aluminum triethylate inxZS .cc. of dry benzene is quickly added'dropwise to, a boiliug solution ,of 0.07 mol of pure 2,4-dinitrophenolin 120cc. .of dry .benzene, ;and.the mixture is-heatedfor 2 hours to theboiling point of the solvent. 7.5 g. of productareobtained after workingup as described in Example 5.

Example 7 Die'thyl-[2,4 dinitronaphthyl f1 aluminum alcoholate Example;8. :Ethyl-b.is-'[2;4-dinitronaphzfhyls( I 1 aluminum alcoholate Asolution of8.1, ;g. of aluminum triethylate"(0;05 mol) in 80 cc. of drybenzene'is quickly added dropwise to a boiling solution -,of 40.95 g.,of. 2,4;g1initro-hnaphthol 10.175. mol) ,in. 400' cc. of ..dry benzeuhi1 us- Themixtureisheatedfor2 to, 10 hours to the. o ling jpoint. of:the solvent, and; the reaction ,product which precipitatesyisfilteredbfi with suction while, still ho t, is again =;subjecte,dtoextraction While. hot with dry,.benzene vfor re- .moving .1.1nreacted.,;2, .-.di nitr.onaphthol and his dried in vacuo afterwashiugtwithqabsoluteaether.. 22, g; .ofsethyl- Example 9.-Butyl-bis-2,4-dinitr0naphthyl-(1 )1- aluminum alcoholate A solution of 5 g. ofaluminum sec. butylate in 50 cc. .of dry benzene is added to a boilingsolution of 14.2 g of 2,4-dinitro-1-naphthol in cc. of dry benzene whilestirring, and the mixture is heated for another 3 hours to the boilingpoint. The reaction product which precipitates is filtered off withsuction while still hot, subjected to extraction with dry benzene whilehot for .removing unreacted 2,4-dinit'ronaphthol and dried in vacuoafter washing with absolute ether. 8.5 g. of sec.butylbis-[2,4-dinitronaphthyl( 1 ]-aluminum alcoholate are obtained,this representing 73.8% of the theoretical yield.

By using aluminum-n-butylate the n-butyl-bis-[ 2,4,-dinitronaphthyl-(1)]-alurn inum alcoholate is obtained.

Example 10.-Isoamyl-bis-[2,4-dinitr0naphthyl-(1 )1- aluminum alcoholateA solution of 6 g. of aluminum isoamylate in- 6 0 c c. of dry benzene isadded to a boiling solutionof 1 -4.6 g. of 2,4dinitr0-1-naphthol in 140cc. of dry benzene and heated for another three hours to theboilingpoint. flihe reaction product which precipitates is worked up asdescribed in Example 9; 10' g. ofisoarnyl-bis-[2,4-dinitronaphthyl-(l)]-aluminum alcoholate are obtained,the yield corresponding to 82.7% of the theoreticalyield.

Example 11.-Is0pr0pyl-bis-[2,4-dinizr0uapl1thyl-(1)]- aluminumalcoholate A solution of-S g. of aluminum isopropylate in 40cc. of1,2-dichloro ethane is addedto a solutionof 11.4 g. of.2,4dinitro-l-naphthol in 60 cc. of 1,2-dichloro-ethane whilestirringaud;heat ed-for another 4 to 6 hours to-the boiling point. The reactionproduct whichprecipitates is frltered off with suction while stillhot,is subjected to .extraction .while hot with dry benzenefiorremovingunreacted,2,4-dinitronaphthol and is driedin ,vaeuo after washing withabsolute ether.

Example 12. Is0pr0pyl-bis-[2,4-dinitr0naphthyl-(1)1- aluminum alcoholate515 g. (2.2 mol) of 2,4-dinitro-1 -naphtholare, .dissplved in 2000 cc.of ,dry benzene. A solution 913:20 4 g. 1;0 moi) of aluminumisopropylate in 750 cc pfdrylpey zepe is slowly added to the solutionmentioned before. reaction mixture is then heated to boiling for about 6to 8 hours whereby the reaction product precipitates. The reactionmixture is filteredofi" with suction while still hot, washed with dryhenzeneand extracted-forabout 20:.h0urs in a SQxhletappar a t-us;withabout 3000 cc. of-dry benzene in;,order to remove unreacted startingmaterials. After this the benzene issucked ofi and thereactionpmductsisdried in vacuo. '5 3.4 1 g.of.isopropyl-bise[2;4sdinitronaphthyI-(UI-aluminum alcoholate are.obtained-inrthe form .ot-orange-colored crystals. Yield: 96.7% -of-sthethem .retical yield.

' fljhe product is obtained by reacting 2,,4-dinitro7l napht o .anaaluminumemhexyl in d y; b nzene/inf. accordance with Example 12.

Example '14. n-jHeptyl-bis- [2,4-diuitr onupltthyl-t1 aluminumalcoholate i Theproduct ise ta sdhy r act n .ilrhd nit a... mo as smiaurunrhsptyle r rytbsnzsse; a with. N amp Example '15.Cyclolzexyl-bis-[2;4-dinitronaph1lzyl-(1 '1- -aluminum alcoholate to a boiling solutionof 25.7 g. (0.11 mol) of 2,4-dinitrol-naphthol in 250 cc. of drybenzene. The reaction mixture is heated to boiling for about 6 hourswhereby the reaction product precipitates. It is sucked otf while hot,washed with dry benzene and extracted with dry benzene in order toremove unreacted starting materials. Then the benzene is sucked oh? andthe reaction product is dried in vacuo. Yield: 27 g. ofcyc1ohexyl-bis-[2,4-dinitronaphthyl-(1)]-aluminum alcoholate, i.e. 91.2%of the theoretical yield, in the form of orange-colored crystals.

What we claim is:

1. The compound of the formula R represents a member selected from thegroup consisting of the alkyl radicals with 2 to 9 carbon atoms and thecyclohexyl radical,

R represents a member selected from the group consisting of the 4-nitrophenyl group, the 2,4-dinitro phenyl group, and the2,4-dinitro-1-naphthyl group, and

R" represents a member selected from the group consisting of the alkylradicals with 2 to 9 carbon atoms, the cyclohexyl radical, the 4-nitrophenyl group, the 2,4-dinitro phenyl group, and the2-4-dinitro-1-naphthyl group.

2. The isopropyl bis [2,4 dinitronaphthyl-(1)]-aluminum alcoholate. i

3. The [2,4-dinitro naphthyl-(1)]-alumnium alcoholates of the formulaon: O-Al-O8NO: AR No, no,

wherein R is an alkyl radical with 2 to 9 carbon atoms.

4. The [2,4-dinitro naphthyl-(1)]-aluminum alcoholates of the formulaOrN80-Al-O N:

wherein R is the cyclohetyl radical. 1 r

5. The ethyl bis-[2,4-dinitro naphthyl-(1)]-aluminum alcoholate.

6. The butyl bis-[2,4-dinitro naphthyl-(1)]-aluminurn alcoholate.

7. The isoamyl bis-[2,4-dinitro naphthyl-(1)]-aluminum alcoholate.

8. The process of producing a compound of the formula RO-Al-O R whichprocess consists in reacting 1 mole of an aluminum trialcoholate of theformula Al(OR) wherein R represents a member selected from the groupconsisting of the alkyl radicals with 2 to 9 carbon atoms and thecyclohexyl radicals, with 1 to 3 moles of a compound selected from thegroup consisting of 4-nitro phenol, 2,4-dinitro phenol, and2,4-dinitro-1-naphthol in the presence of a solvent at a temperature notexceeding the boiling point of the reaction mixture, and filtering offthe resulting reaction product.

9. The process according to claim 8 in which the aluminum tri-alcoholateis reacted with 1-3- moles of 2,4-dinitro-l-naphthol.

10. The process according to claim 8, in which the solvent is anaromatic hydrocarbon selected from the group consisting of benzene,toluene and xylene.

References Cited in the file of this patent FOREIGN PATENTS GreatBritain June 1, 1955 OTHER REFERENCES Mehrotra: Journ. Indian Chem.Soc., vol. 30, No. 9 (1953), pp. 585 to 591.

1. THE COMPOUND OF THE FORMULA